CN106536042B - Carbon monoxide-olefin polymeric without precious metal - Google Patents

Carbon monoxide-olefin polymeric without precious metal Download PDF

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CN106536042B
CN106536042B CN201580038986.4A CN201580038986A CN106536042B CN 106536042 B CN106536042 B CN 106536042B CN 201580038986 A CN201580038986 A CN 201580038986A CN 106536042 B CN106536042 B CN 106536042B
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CN106536042A (en
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拉尔斯·汉斯根
卡尔·谢尔曼茨
克劳斯·斯托
维克多·沃尔夫
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Treibacher Industrie AG
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Abstract

The composition of Formulas I, Ce1‑a‑b‑cNaMbDcOxWherein M represents more than one elements of alkali metal group in addition to sodium to I, and N is Bi and/or Sb, and D exists or is not present, if it is present being selected from Mg, Ca, Sr, Ba；Y,La,Pr,Nd,Sm,Gd,Er；One or more of Fe, Zr, Nb, Al；A is the number in the range of 0 < a≤0.9, and b is the number in the range of 0 <b≤0.3, and c is the number in the range of 0≤c≤0.2；A adds b that c is added to be < 1, and x is the purposes of the number and its exhausted gas post-processing system for being used for diesel engine, gasoline engine, lean-combustion engine and power plant in the range of 1.2≤x≤2.

Description

Carbon monoxide-olefin polymeric without precious metal
Technical field
The present invention relates to carbon monoxide-olefin polymerics without precious metal, are such as useful for the oxidation of particle matter (PM) 's.
Background technique
The exhaust gas of diesel engine contains the PM that can cause environmental problem.In order to capture PM, diesel particulate filter is devised Device (DPF) filters PM in the diesel particulate filter (DPF) from exhaust gas.Most common DPF type is by SiC or violet Ceramic wall-flow filter made of green stone.Since the PM of aggregation accumulates in this filter, so back pressure is gradually increased, hair The power of motivation gradually decreases.Therefore by wall-flow filter continuously (passively) and/or discontinuously (active) regeneration with After-flame coal smoke is (referring to such as A.P.Walker et al., Controlling particulate emissions from The 28th phase of Diesel vehicles, Topics in Catalysis, 2004,165-170)).
For example, describing in US 8,114,354, for passive regeneration, filter must not be repaired without catalyst composition Mend washcoat layer.The element of this group including Al, Ce, Zr, Si, zeolite, alkali metal and noble metal catalyst composition by NO It is oxidized to NO2, it is a kind of oxidant for being better than oxygen for coal smoke.Actively non-catalytic regeneration operates at about 650 DEG C.In bavin Direct postinjection fuel is the most common method for reaching the temperature before oil machine oxidation catalyst (DOC).Postinjection method Have the shortcomings that increase fuel consumption and dilutes automobile oil.
According to the description that S.Spiess is provided in CAPoC9 (in August, 2012), gasoline direct vehicle is obtaining market Share, to reach new CO2Discharge limitation.By this new technology, fuel consumption and CO can be reduced2Discharge, but the vehicle Significantly more particle is discharged than conventional gasoline engin, and the particle discharged is 10 times of Novel diesel engine.This pollution can To be prevented with gasoline particles filter, the discharge of particle can be significantly reduced.
Have been made make great efforts with provide be used at a lower temperature together with oxygen catalysis oxidation PM with reduce actively again The amount and the catalyst of reproduction time of raw circulation.Thus, it is possible to reduce fuel consumption and the maneuverability of automobile oil can be increased Energy.
A variety of mixed oxides without precious metal are disclosed in DE 102 00 900 2182 for soot oxidation.It is public The oxide based on iron, chromium and cobalt is opened.
EP 2 210 861 is related to diesel particulate filter comprising the cerium compound oxide with Bi and Pr, The molar ratio of middle Ce, Bi, Pr are expressed as Ce:Bi:Pr=(1-x-y): x:y.Wherein 0 < x≤0.3 and 0 < y≤0.5.
In US 8,071,501, describe including composite oxides and platinum group metal (PGM, wherein PGM include Ru, Rh, Pd, Os, Ir and Pt) exhaust gas purifying catalyst, wherein composite oxides are by Ce, Bi and the lanthanide series group in addition to La and Ce At.In EP 2 269 730, other elements selected from the periodic table of elements the 3rd, 4 and 13 races have expanded this based composite oxide.
In US 2009/0288401, disclose the composite oxides for exhaust gas purifying catalyst, containing Ce, Bi and More than one are selected from the element of the alkaline-earth metal in addition to beryllium.In addition, more than one other elements can be selected from Zr, Pr and Tb.
The composite oxides of the perovskite type for soot oxidation have been claimed in EP 1 829 609.These perovskites Ingredient can use formula R TO3It indicates, wherein R includes more than one yuan selected from the group being made of La, Sr, Ba, Ca and Li Element；And T includes more than one elements selected from the group being made of Mn, Fe, Co, Cu, Zn, Ga, Zr, Mo, Mg, Al and Si.
The catalyst for aoxidizing coal smoke is described in WO 2006/044822 (EP 1 817 096), by alkali gold Category, cerium, oxygen and optional platinum group metal and/or zirconium composition.The most active material of description is the combination of cerium and potassium or cerium and caesium.
In Kripasindhu Sardar et al.,, Nanocrystalline Cerium-Bismuth Oxides: Synthesis,Structural Characterization,and Redox Properties“,Chemistry of Materials, the 22nd phase, No. 22, November 23 (2010-11-23) in 2010, the 6191-6201 pages, ISSN:0897- In 4756, doi:10.1021/cm1025848, the cerium with sodium background level-bismuth mixed oxide is described.
The composite oxides for exhaust gas purifying catalyst are disclosed in EP 2 098289, containing Ce, Bi and it is a kind of with The upper element selected from Mg, Ca, Sr and Ba.The catalyst is disclosed as being suitable for the PM of after-flame diesel exhaust at low temperature, and Hardly it is poisoned due to sulphur oxidation.
Summary of the invention
Composition disclosed in the prior art for catalysis oxidation PM is not able to satisfy catalytic performance, supports to sulphur compound The stability of drag and/or resistance hydro-thermal process is required.Therefore, it is an object of the present invention to provide one kind for being catalyzed oxygen Change PM new compositions, have the catalytic activity higher than prior art material, show higher hydrothermal stability and its It is environmental-friendly.
On the one hand, the present invention provides the composition of Formulas I,
Ce1-a-b-cNaMbDcOx I
Wherein
M represents more than one elements of the alkali metal group in addition to sodium, preferably potassium,
N be Bi and/or Sb, preferably Bi,
D exists or is not present, if it is present selected from one or more of following element
-Mg,Ca,Sr,Ba；It is preferred that Ca, Sr, Ba；More preferable Sr,
-Y,La,Pr,Nd,Sm,Gd,Er；It is preferred that Y, Pr, La, Nd；More preferable Pr,
-Fe,Zr,Nb,Al；On the one hand preferred Fe, the preferred Al of another aspect,
A is 0 < a≤0.9, the number in such as range of 0.01≤a≤0.9,
B is 0 <b≤0.3, such as 0.01≤b≤0.3, the number in the range of such as 0.1≤b≤0.2,
C is 0≤c≤0.2, the number in the range of preferably 0≤c≤0.1；
A adds b that c is added to be < 1, and
X is the number in the range of 1.2≤x≤2.
On the other hand, in the composition of Formulas I, there are D.
On the other hand, in the composition of Formulas I, D is not present, and in this aspect, the present invention provides the groups with Formula II Close object
Ce1-a-bNaMbOx II
Wherein
M represents more than one elements of the alkali metal group in addition to sodium,
N is Bi and/or Sb,
A is the number in the range of 0 < a≤0.9,
B is the number in the range of 0 <b≤0.3,
A adds b to be < 1, and
X is the number in the range of 1.2≤x≤2.
On the other hand, the present invention provides compositions, selected from the group being made of following composition:
Bi0.45Ce0.45K0.10O1.65-1.4,
Bi0.40Ce0.40K0.20O1.4-1.2,
Bi0.30Ce0.60K0.10O1.7-1.4,
Bi0.80Ce0.10K0.10O1.5-1.4,
Bi0.10Ce0.80K0.10O1.8-1.4,
Bi0.4Ce0.4K0.1Sr0.1O1.55-1.35,
Bi0.4Ce0.4K0.1Pr0.1O1.6-1.4, and
Bi0.4Ce0.4K0.1Fe0.1O1.6-1.4。
Specific embodiment
The composition of such as Formulas I provided by the invention is referred to herein as " (according to) composition of the invention ".
For the purpose of specification and claims, term " alkali metal " refers to alkali metal in addition to sodium or alkali metal Mixture, such as mixture more than a kind of alkali metal element.According to IUPAC, alkali metal is the member of the 1st race of the periodic table of elements Element.
On the other hand, the present invention provides the methods for being used to prepare composition according to the present invention, to use polymerization Complex compound method is characterized, wherein preferably passing through the metal ion of polyesterification connection complexing by polymerization.
Method provided by the invention is referred to herein as " (according to) method of the invention ".
Polymer complex method for the preparation of the compounds of the present invention is (such as to exist similar to Pechini method A.L.Quinelato et al., " Synthesis and sintering of ZrO2-CeO2powder by use of Polymeric precursor based on Pechini process ", Journal of Material Science the 36th Phase, similar method described in 2001,3825-3830) method.
More particularly, the method for the present invention includes the following steps:
A) particularly by the way that bismuth oxide to be dissolved in nitric acid and with water, more than one polymer precursors and optional one kind The mixture dilute solution of the above complexing agent prepares bismuth salt in water, inorganic acid, more than one polymer precursors and optional one Kind or more solution in the mixture of complexing agent,
B) particularly by by cerium salt, basic salt and more than one optional such as the D defined in the compound of Formulas I Salt is dissolved in the mixture of water, more than one polymer precursors and more than one optional complexing agents and prepares cerium salt, alkali Property salt and optional more than one salts such as the D defined in the compound of Formulas I water, more than one polymer precursors and Solution in more than one optional complexing agents,
C) inorganic acid is added in the solution optionally obtained to step b),
D) metallic solution obtained a) and b) or under a) and c) is blended under stirring or vortex, and
E) in air at 300 to 1000 DEG C, within the temperature range of preferably 350 DEG C to 600 DEG C, most preferably 375-500 DEG C, If 400 DEG C of heat treatments are in d) middle solution 1 to 120 hour obtained, preferably 1 to 50 hour, more preferable 4 to 10 hours, such as 5 is small When, with a holding temperature preferably in 70-120 DEG C of temperature range and more electedly in 120-250 DEG C of temperature range The second interior holding temperature.
In the method for the invention, complexing agent is also used as organic solvent.
In the method for the invention, polymer precursor is also used as organic solvent.
In the method for the invention, suitable polymer precursor can be used for step a) and b) in, it is preferable that it is identical poly- Polymer precursor can be used for step a) and b) in.Suitable polymer precursor includes polybasic carboxylic acid class, hydroxycarboxylic acid, polyalcohol Class and its mixture, preferred polyol class and polybasic carboxylic acid class and its mixture, more preferable polyalcohols.Most preferably, by second Glycol is used as polymer precursor.
In the method for the invention, suitable complexing agent can be used for step a) and b) in, it is preferable that identical complexing agent Can be used for step a) and b) in.Suitable complexing agent includes organic compound, such as organic acid, ketone, aldehydes, alcohols, Amine and its mixture, preferably polybasic carboxylic acid class, more preferable citric acid and oxalic acid, most preferably citric acid.Complexing agent can increase The solubility of metal salt and the uniformity being crosslinked and Metal Distribution in polymer gel can also be increased in polymer architecture.
In the method for the invention, suitable basic salt includes the salt of the alkali metal in addition to sodium, such as Nitrates, oxygen Compound class, hydroxide species, carbonate, Sulfates, Acetates, halogenation species, preferably nitrate class and carbonate, Most preferably Nitrates.
In the method for the invention, step a) and c) in inorganic acid include suitable inorganic acids, such as nitric acid, sulphur Acid, hydrochloric acid and its mixture, more preferable nitric acid, sulfuric acid and its mixture, most preferably nitric acid.
Only with polyalcohols as polymer precursor without complexing agent or another polymer precursor in the case where, Preferably by oxidisability inorganic acid (such as nitric acid) be used as inorganic acid a part of polyalcohols is oxidized to polybasic carboxylic acid class, this It is suitable for the polyesterification with non-oxide polynary acids.By using the mixture of polyalcohols and polybasic carboxylic acid class, inorganic acid without It need to be oxidizing acid to open polymerization.
It was surprisingly found that composition of the invention shows the catalysis for being used to aoxidize PM higher than prior art material Activity.
It is (aobvious that excellent catalytic activity is shown in the composition (calcining at 400 DEG C) of the invention that state is just made It is shown as lower T50Value), far more than the activity (as can be seen from Table 2) of prior art material.By to CeBiOxBody The alkali metal (preferably potassium) that system introduces in addition to sodium can increase oxidation compared with the material of the bismuth containing cerium disclosed in the prior art The catalytic activity of PM.The T of cerium bismuth alkalinity mixed oxide of the invention50Value (at 200 DEG C and terminates to observe between temperature The temperature of 50% mass loss) up to 110 DEG C, lower than the compound of the bismuth containing cerium of comparative examples, this is from the embodiment 4 of table 2, right Than being apparent in example 2.
And, it has therefore been surprisingly found that composition according to the present invention shows up to 800 DEG C of high thermal stability.This The heat ageing composition of invention shows the catalytic activity for soot oxidation higher than prior art material, this is again from table 2 In be apparent.The T of composition (cerium bismuth alkalinity mixed oxide) of the invention50Value is up to 115 DEG C, lower than containing for comparative examples The Comparative composition of cerium bismuth, this is apparent such as from the embodiment 2 of table 2 and comparative examples 3.
Surprisingly, potassium sill is just being made state and is showing under ageing state more mixed than sodium base cerium bismuth alkalinity Close the high activity of oxide material.The T of composition (cerium bismuth alkalinity mixed oxide) of the invention50Value is in the case where being just made state Up to 71 DEG C, it is lower than cerium bismuth sodium comparative examples, this is apparent such as from the embodiment 4 of table 2 and comparative examples 1.Moreover, aging Afterwards, the T of composition of the invention (cerium bismuth alkalinity mixed oxide)50Value is lower than cerium bismuth sodium comparative examples, this is such as up to 65 DEG C It is apparent from the embodiment 2 and comparative examples 1 of table 2.If there is D in the present compositions, shape is just being made Activity under state can be further improved.
Due to the higher catalytic activity of composition of the invention, temperature can be reduced in the normal assays stage Have been able to the range reached.Therefore, the amount of the fuel of the postinjection for initiative regeneration can be reduced.
Because the exhaust gas of internal combustion engine contains a certain amount of water, another importance of the invention is hydrothermal stability. Basic matterial hydrolabil disclosed in the prior art (such as EP 1 817 096).It surprisingly sends out according to the present invention Existing, by the way that bismuth to be introduced into the system of bismuth alkalinity mixed oxide, system shows the stability to hydro-thermal process enhancing.
Furthermore, it has therefore been surprisingly found that compared with prior art material, composition of the invention is directed to after hydrothermal aging Soot oxidation needs lower temperature.The T of composition (cerium bismuth alkalinity mixed oxide) of the invention after hydro-thermal process50Value Up to 96 DEG C, it is lower than cerium potassium system (referring to embodiment 1, the comparative examples 5 of table 3).Think that this respect is attributed to prior art material In free potassium substance (referring to Fig. 1).In contrast, free potassium substance is not observed in the present compositions (referring to figure 2)。
Composition of the invention is the first basic catalyst for being used to aoxidize PM for showing hydrothermal stability.
Composition of the invention is by the high catalytic activity for being used for soot oxidation of basic matterial and without the water of basic matterial The first catalyst composition that thermal stability combines.
Composition of the invention can be used alone or the support materials knot with coating or extrusion form for DPF system It closes and uses.In such an embodiment, composition of the invention also can be used alone or with the particle for petrol engine The load of filter is used together.
Composition according to the present invention can be used advantageously in conjunction with SCR- catalyst with when SCR to be applied on DPF In the exhaust after-treatment of diesel engine and lean-combustion engine.
Composition of the invention can be used for removing in the application of coal smoke, especially for diesel engine and gasoline engine Exhausted gas post-processing system, and in addition, composition of the invention can also be used for other applications, such as removing power plant (is such as changed Stone fuel power plant or biomass power plant) in PM.
On the other hand, the present invention provides compositions of the invention starts for such as diesel engine, gasoline engine, lean-burn The purposes of the exhausted gas post-processing system in machine and power plant.
Characterization
Composition of the invention has carried out characterizing part according to XRD.
Using the PANalytical X ' Pert PRO system with the Ni copper radiation filtered, (wavelength is 1.5406 HeCu-K α 1 and Cu-K α 2 it is bimodal) obtain powder X-ray RD (X-ray diffraction) pattern.The instrument is with PIXcel Prague-Franz Brentano-geometry (Bragg-Brentano-geometry) in operation.
Catalysis test for PM removal efficiency, makes composition be subjected to catalytic powder test condition as described below.
Condition for catalytic powder test
Sample preparation
By synthesis of solid sample of the invention hand-ground in the agate mortar.By powder sample and carbon black (CB, Printex 90, Evonik Degussa GmbH (method A) or CB, Printex U, Evonik Carbon Black GmbH (method B)) it is carefully mixed until mixture uniformly to form loose contact mode with the mass ratio of 4:1 with scuppit.
Measure catalytic activity
It is recorded by two different methods by Thermogravimetric Data and carries out characteristic soot combustion temperatures (T50Value, that is, exist 200 DEG C and terminate to observe the temperature of 50% mass loss between temperature) measurement.
Method AIt is carried out with 1 synchronous solving of TGA/DSC (Mettler Toledo Corp.).By 8%O2、350ppm CO, 250ppm NO, 50ppm propane, 50ppm SO2With the N as surplus2Mixture be used as model charge gas.Total air flow is 50ml/min.It measures and urges under the dynamic condition of the heating rate with 10 DEG C/min within the temperature range of 25 DEG C to 700 DEG C The soot combustion activity of agent.
Method BIt is carried out with NETSCH STA 409C/CD.By 20%O2In N2In mixture be used as model charge gas.Always Air-flow is 50ml/min.It is surveyed under the dynamic condition of the heating rate with 5 DEG C/min within the temperature range of 25 DEG C to 700 DEG C Measure the soot combustion activity of catalyst.
Test for thermal stability makes composition be subjected to being used for the condition of heat ageing as follows.
Condition for heat ageing
Grape berry is carried out by calcining 2 hours to powder sample at 800 DEG C in traditional Muffle furnace.
Test for hydrothermal stability makes catalyst composition be subjected to hydrothermal pretreatment as described below.
Condition for hydrothermal pretreatment
Hydrothermal pretreatment carries out in the heavy multi-chamber in 7 with teflon inlet (multiclave) of customization.It will be made Standby sample (100-120mg) is suspended in 10ml deionized water (fill level: 33%).Autoclave is heated to 150 DEG C.It will Multi-chamber rotates 60 minutes at 150 DEG C along its cylindrical shaft in an oven, and is cooled to room temperature it again.It will be through hydrothermal aging Sample separate with liquid, be washed with deionized and at 60 DEG C and depressurize under (< 10 millibars) in vacuum drying oven by filtering Middle drying.
More detailed description of the present invention
The present invention is explained in greater detail referring now to embodiment and comparative examples, but the present invention is not limited to these.It is aobvious The temperature shown is degree Celsius (DEG C).
Synthesis
Embodiment 1
Bi0.45Ce0.45K0.10O1.65-1.4It is synthesized by polymer complexes sol-gal process.
The mixture that 50 deionized waters, 33.46ml ethylene glycol (EG) and 47.285g citric acid monohydrate close object (CA) is used as Solvent.
By bismuth oxide-(III) (Bi of 0.1048g of stoichiometry2O3) be dissolved in 0.1477ml concentrated nitric acid (69%) simultaneously The H of 0.704ml is added2O/EG/CA mixture is (in Bi2O3After dissolution, white precipitate can be formed, which is being added H2It is dissolved after O/EG/CA mixture).By cerous nitrate-(III) hexahydrate (0.1954g Ce (NO3)3*6H2O it) is dissolved in The H of 0.842ml2In O/EG/CA mixture and 9 μ l concentrated nitric acids (69%) are added.By potassium nitrate (0.0101g KNO3) be dissolved in The H of 0.187ml2In O/EG/CA mixture and 2 μ l concentrated nitric acids (69%) are added.Three kinds of solution of acquisition are mixed merga pass to determine Rail oscillator vortex oscillation 60 minutes.Then the solvent of solution is evaporated and calcines the evaporated residue of acquisition in air. In order to evaporate solvent, solution is heated to 90 DEG C from room temperature with 10 DEG C/h of the rate of heat addition.Stopped at 90 DEG C at 5 hours After staying the time, 200 DEG C are heated the mixture to 5 DEG C/h of the rate of heat addition.Keep the temperature after 5 hours, with 10 DEG C/it is small When the rate of heat addition heat the sample to 400 DEG C.Sample is calcined 5 hours at 400 DEG C.By the oxide powder of calcining with 20 DEG C/h rate be cooled to room temperature and (sample be just made).
Embodiment 2 to 5
The composition that embodiment 2 to 5 is related to is and public to be similar to institute in embodiment 1 as disclosed in following table 1A and 1B The program preparation opened, but use suitable raw material and amount.The amount for the raw material being used to prepare according to embodiment 2 to 5 be listed in table 1A and In 1B.The mixture that 50ml deionized water, 33.46ml ethylene glycol (EG) and 47.285g citric acid monohydrate close object (CA) is used as Solvent.
Table 1A
Table 1B
*) for dissolving Bi2O3
*) for dissolving other metal salts
Embodiment 6
Bi0.4Ce0.4K0.1Sr0.1O1.55-1.35It is synthesized by polymer complexes sol-gal process.
200ml deionized water, 133.84ml ethylene glycol (EG) and 189.14g citric acid monohydrate are closed to the mixture of object (CA) As solvent.
By bismuth oxide-(III) (Bi of 5.26g of stoichiometry2O3) be dissolved in the concentrated nitric acid (69%) of 11.81g and add Enter the H of 40.77g2O/EG/CA mixture is (in Bi2O3After dissolution, white precipitate can be formed, which is being added H2O/ It is dissolved after EG/CA mixture).By cerous nitrate-(III) hexahydrate (9.81g Ce (NO3)3*6H2O), potassium nitrate (0.57g KNO3) and strontium carbonate (0.83g SrCO3) it is dissolved in the H of 59.52g2In O/EG/CA mixture and 0.85g concentrated nitric acid is added (69%).Two kinds of solution of acquisition are mixed 60 minutes by magnetic stirring apparatus.Then the solvent of solution is evaporated and will be obtained Evaporated residue calcine in air.In order to evaporate solvent, solution is heated from room temperature with 7.5 DEG C/h of the rate of heat addition To 70 DEG C.At 70 DEG C after 24 hours residence times, 200 DEG C are heated the mixture to 26 DEG C/h of the rate of heat addition. It keeps the temperature after 24 hours, heats the sample to 400 DEG C with 200 DEG C/h of the rate of heat addition.Sample is forged at 400 DEG C It burns 5 hours.The oxide powder of calcining is cooled to room temperature with 20 DEG C/h of rate and (sample is just made).
Embodiment 7
Bi0.4Ce0.4K0.1Pr0.1O1.6-1.4It is synthesized by polymer complexes sol-gal process.
200ml deionized water, 133.84ml ethylene glycol (EG) and 189.14g citric acid monohydrate are closed to the mixture of object (CA) As solvent.
By bismuth oxide-(III) (5.09g Bi of stoichiometry2O3) be dissolved in 11.81g concentrated nitric acid (69%) and be added 39.12g H2O/EG/CA mixture is (in Bi2O3After dissolution, white precipitate can be formed, which is being added H2O/EG/ It is dissolved after CA mixture).By cerous nitrate (III) hexahydrate (9.48g Ce (NO3)3*6H2O), potassium nitrate (0.55g KNO3) With praseodymium nitrate hexahydrate (2.37g Pr (NO3)3*6H2O) it is dissolved in the H of 59.52g2Simultaneously 0.85g is added in O/EG/CA mixture Concentrated nitric acid (69%).Two kinds of solution of acquisition are mixed 60 minutes by magnetic stirring apparatus.Then simultaneously by the solvent evaporation of solution The evaporated residue of acquisition is calcined in air.In order to evaporate solvent, by solution with 7.5 DEG C/h of the rate of heat addition from room Temperature is heated to 70 DEG C.At 70 DEG C after 24 hours residence times, heated the mixture to 26 DEG C/h of the rate of heat addition 200℃.It keeps the temperature after 24 hours, heats the sample to 400 DEG C with 200 DEG C/h of the rate of heat addition.By sample 400 It is calcined 5 hours at DEG C.The oxide powder of calcining is cooled to room temperature with 20 DEG C/h of rate and (sample is just made).
Embodiment 8
Bi0.4Ce0.4K0.1Fe0.1O1.6-1.4It is synthesized by polymer complexes sol-gal process.
200ml deionized water, 133.84ml ethylene glycol (EG) and 189.14g citric acid monohydrate are closed to the mixture of object (CA) As solvent.
By bismuth oxide-(III) (Bi of 5.33g of stoichiometry2O3) be dissolved in 11.81g concentrated nitric acid (69%) and be added 41.03g H2O/EG/CA mixture is (in Bi2O3After dissolution, white precipitate can be formed, which is being added H2O/EG/ It is dissolved after CA mixture).By cerous nitrate (III) hexahydrate (9.94g Ce (NO3)3*6H2O), potassium nitrate (0.58g KNO3) With ferric nitrate (III) nonahydrate (2.31g Fe (NO3)3*9H2O) it is dissolved in the H of 59.52g2O/EG/CA mixture is simultaneously added 0.85g concentrated nitric acid (69%).Two kinds of solution of acquisition are mixed 60 minutes by magnetic stirring apparatus.Then the solvent of solution is steamed It sends out and calcines the evaporated residue of acquisition in air.In order to evaporate solvent, by solution with 7.5 DEG C/h of the rate of heat addition 70 DEG C are heated to from room temperature.At 70 DEG C after 24 hours residence times, the rate of heat addition with 26 DEG C/h adds mixture Heat is to 200 DEG C.It keeps the temperature after 24 hours, heats the sample to 400 DEG C with 200 DEG C/h of the rate of heat addition.Sample is existed It is calcined 5 hours at 400 DEG C.The oxide powder of calcining is cooled to room temperature with 20 DEG C/h of rate and (sample is just made).
Comparative examples 1
Bi0.45Ce0.45Na0.10O1.65-1.4It is synthesized by polymer complexes sol-gal process.
The mixture that 50ml deionized water, 33.46ml ethylene glycol (EG) and 47.285g citric acid monohydrate close object (CA) is used Make solvent.
By bismuth oxide-(III) (Bi of 0.1048g of stoichiometry2O3) be dissolved in 0.1477ml concentrated nitric acid (69%) simultaneously The H of 0.704ml is added2O/EG/CA mixture is (in Bi2O3After dissolution, white precipitate can be formed, which is being added H2It is dissolved after O/EG/CA mixture).By cerous nitrate-(III) hexahydrate (0.1954g Ce (NO3)3*6H2O it) is dissolved in The H of 0.842ml2In O/EG/CA mixture and 9 μ l concentrated nitric acids (69%) are added.By sodium nitrate (0.0085g NaNO3) be dissolved in The H of 0.187ml2In O/EG/CA mixture and 2 μ l concentrated nitric acids (69%) are added.Three kinds of solution of acquisition are mixed merga pass to determine Rail oscillator vortex oscillation 60 minutes.Then the solvent of solution is evaporated and calcines the evaporated residue of acquisition in air. In order to evaporate solvent, solution is heated to 70 DEG C from room temperature with 7.5 DEG C/h of the rate of heat addition.At 24 hours at 70 DEG C After residence time, 200 DEG C are heated the mixture to 26 DEG C/h of the rate of heat addition.Keep the temperature after 24 hours, with 200 DEG C/h the rate of heat addition heat the sample to 400 DEG C.Sample is calcined 5 hours at 400 DEG C.By the oxidate powder of calcining End is cooled to room temperature with 20 DEG C/h of rate and (sample is just made).
Comparative examples 2
Bi10Ce80Sr10Ox(2 438 984 A1 of EP, embodiment 2)
By the metal nitrate (Ce (NO of 0.5988g3)3*6H2O, the Bi (NO of 0.0836g3)3*5H2The Sr of O and 0.0365g (NO3)2) mixing, the molar ratio of Ce/Bi/Sr=0.8/0.1/0.1 is formed, and 5ml deionized water is added.After nitrate dissolution, White precipitate is formed, and 3ml concentrated nitric acid (69%) is added.Mixture obtained is stirred until obtaining clear solution.To acquisition Solution in be added again water make final solution total volume be 50ml.It is slowly added to while stirring into the solution of acquisition 40ml precipitating reagent (1 mole of ammonium carbonate aqueous solution).The suspension of acquisition is futher stirred 30 minutes.Sediment is obtained, will be sunk Starch filtering is washed with deionized and dries 15 hours in air atmosphere at 125 DEG C.By dried solid 400 It is calcined 5 hours at DEG C.
Comparative examples 3
Bi10Ce50Pr40Ox(2 210 861 B1 of EP, embodiment 1)
Firstly, by 0.6809g praseodymium oxide (Pr6O11, 99.9%, ABCR) and it is dissolved in 4.5ml concentrated nitric acid (69%).So Afterwards, by 2.1711g cerous nitrate hexahydrate (Ce (NO3)3*6H2O, 99.9%, ChemPur) and 0.485 bismuth nitrate pentahydrate (Bi(NO3)3*5H2O, >=99.99%, Sigma-Aldrich) it is added in the nitric acid solution of Pr, form Ce/Bi/Pr=0.5/ 0.1/0.4 molar ratio.It is slowly added to 45ml precipitating reagent (1 mole of carbon into solution obtained while stirring in 30 minutes Sour aqueous ammonium).The sediment of acquisition is filtered and is washed with deionized, is dried 15 hours in air at 125 DEG C.It will The dried solid obtained is calcined 5 hours at 400 DEG C.
Comparative examples 4
Ce50K50Ox(WO 2006/04482)
Comparative examples 3 are prepared by melting corresponding nitrate.For the comparative examples, by the Ce of 1.0856g (NO3)3*6H2The KNO of O and 0.2528g3Hand mix.The mixture of acquisition is added with 50 DEG C/h of the rate of heat addition from room temperature Heat is to 350 DEG C.350 DEG C of temperature is kept constant 12 hours, room temperature is then again lowered to 120 DEG C/h of rate.It will The solid of acquisition is calcined 5 hours at 400 DEG C.
Comparative examples 5
Ce50K50Ox(2006/044822 A1 of WO) is by by 4.3422g Ce (NO3)3*6H2O be dissolved in 10ml go from 0.6910g K is added in sub- water and into Ce aqueous solution2CO3Synthesis.Subtracted by evaporating 24 hours in air at 120 DEG C The volume of the solution of small acquisition.The drying solid of acquisition is calcined 5 hours at 400 DEG C.
Comparative examples 6
Ce66.7K33.3Ox(WO 2006/044822A1) is prepared by melting corresponding nitrate.For the comparison Example, by the Ce (NO of 1.7369g3)3*6H2The KNO of O and 0.2022g3Hand mix.By the mixture of acquisition with 50 DEG C/h The rate of heat addition be heated to 350 DEG C from room temperature.350 DEG C of temperature is kept constant 12 hours, then with 120 DEG C/h of speed Rate is again lowered to room temperature.The solid of acquisition is calcined 5 hours at 400 DEG C.
Comparative examples 7
Ce66.7K33.3Ox(WO 2006/044822A1) is by by 4.3422g Ce (NO3)3*6H2O is dissolved in 10ml and goes 0.3455g K is added in ionized water and into Ce aqueous solution2CO3Synthesis.By being evaporated in air at 120 DEG C 24 hours Reduce the volume of the solution obtained.The drying solid of acquisition is calcined 5 hours at 400 DEG C.
Comparative examples 8
Bi0.45Ce0.45Sr0.1OxIt is synthesized by polymer complexes sol-gal process.
200ml deionized water, 133.84ml ethylene glycol (EG) and 189.14g citric acid monohydrate are closed to the mixture of object (CA) As solvent.
By bismuth oxide-(III) (Bi of 5.17g of stoichiometry2O3) be dissolved in the concentrated nitric acid (69%) of 11.81g and add Enter the H of 39.77g2O/EG/CA mixture is (in Bi2O3After dissolution, white precipitate can be formed, which is being added H2O/ It is dissolved after EG/CA mixture).By cerous nitrate-(III) hexahydrate (9.64g Ce (NO3)3*6H2) and strontium carbonate (0.71g O SrCO3) it is dissolved in the H of 59.52g2In O/EG/CA mixture and 0.85g concentrated nitric acid (69%) is added.By two kinds of solution of acquisition It is mixed 60 minutes by magnetic stirring apparatus.Then the solvent of solution is evaporated and forges the evaporated residue of acquisition in air It burns.In order to evaporate solvent, solution is heated to 70 DEG C from room temperature with 7.5 DEG C/h of the rate of heat addition.At 24 hours at 70 DEG C Residence time after, heat the mixture to 200 DEG C with 26 DEG C/h of the rate of heat addition.Keep the temperature after 24 hours, with 200 DEG C/h of the rate of heat addition heats the sample to 400 DEG C.Sample is calcined 5 hours at 400 DEG C.By the oxide of calcining Powder is cooled to room temperature with 20 DEG C/h of rate and (sample is just made).
Comparative examples 9
Bi0.45Ce0.45Pr0.1OxIt is synthesized by polymer complexes sol-gal process.
200ml deionized water, 133.84ml ethylene glycol (EG) and 189.14g citric acid monohydrate are closed to the mixture of object (CA) As solvent.
By bismuth oxide-(III) (5.23g Bi of stoichiometry2O3) be dissolved in 11.81g concentrated nitric acid (69%) and be added 40.26g H2O/EG/CA mixture is (in Bi2O3After dissolution, white precipitate can be formed, which is being added H2O/EG/ It is dissolved after CA mixture).By cerous nitrate (III) hexahydrate (9.38g Ce (NO3)3*6H2) and praseodymium nitrate hexahydrate O (2.09g Pr(NO3)3*6H2O) it is dissolved in the H of 59.52g2Simultaneously 0.85g concentrated nitric acid (69%) is added in O/EG/CA mixture.It will obtain The two kinds of solution obtained pass through magnetic stirring apparatus and mix 60 minutes.Then by the evaporation of the solvent of solution and by the evaporated residue of acquisition It calcines in air.In order to evaporate solvent, solution is heated to 70 DEG C from room temperature with 7.5 DEG C/h of the rate of heat addition.At 70 DEG C Under after 24 hours residence times, heat the mixture to 200 DEG C with 26 DEG C/h of the rate of heat addition.Keep the temperature 24 After hour, 400 DEG C are heated the sample to 200 DEG C/h of the rate of heat addition.Sample is calcined 5 hours at 400 DEG C.It will forge The oxide powder of burning is cooled to room temperature with 20 DEG C/h of rate and (sample is just made).
Comparative examples 10
Bi0.45Ce0.45Fe0.1OxIt is synthesized by polymer complexes sol-gal process.
200ml deionized water, 133.84ml ethylene glycol (EG) and 189.14g citric acid monohydrate are closed to the mixture of object (CA) As solvent.
By bismuth oxide-(III) (Bi of 5.03g of stoichiometry2O3) be dissolved in 11.81g concentrated nitric acid (69%) and be added 38.7g H2O/EG/CA mixture is (in Bi2O3After dissolution, white precipitate can be formed, which is being added H2O/EG/ It is dissolved after CA mixture).By cerous nitrate (III) hexahydrate (9.38g Ce (NO3)3*6H2O it) is hydrated with ferric nitrate (III) nine Object (1.94g Fe (NO3)3*9H2O) it is dissolved in the H of 59.52g2Simultaneously 0.85g concentrated nitric acid (69%) is added in O/EG/CA mixture.It will The two kinds of solution obtained are mixed 60 minutes by magnetic stirring apparatus.Then the solvent of solution is evaporated and remains the evaporation of acquisition Object is calcined in air.In order to evaporate solvent, solution is heated to 70 DEG C from room temperature with 7.5 DEG C/h of the rate of heat addition.70 At DEG C after 24 hours residence times, 200 DEG C are heated the mixture to 26 DEG C/h of the rate of heat addition.Keep the temperature After 24 hours, 400 DEG C are heated the sample to 200 DEG C/h of the rate of heat addition.Sample is calcined 5 hours at 400 DEG C.It will The oxide powder of calcining is cooled to room temperature with 20 DEG C/h of rate and (sample is just made).
It is catalyzed the result of test
Table 2 show just be made state (with 400 DEG C/2 hours calcine) and powder used after heat ageing with 800 DEG C/2 hours Method A measurement according to embodiment 1 to 6 prepare cerium-bismuth-alkaline compositions PM removal efficiency of the invention and for pair Than the PM removal efficiency of example 1 and 2.
Table 2
Sample Composition T50Made of just [DEG C] T50[DEG C] of aging
Embodiment 1 Bi0.45Ce0.45K0.10O1.65-1.4 515 535
Embodiment 2 Bi0.40Ce0.40K0.20O1.4-1.2 510 519
Embodiment 3 Bi0.30Ce0.60K0.10O1.7-1.4 520 536
Embodiment 4 Bi0.80Ce0.10K0.10O1.5-1.4 498 563
Embodiment 5 Bi0.10Ce0.80K0.10O1.8-1.4 535 547
Comparative examples 1 Bi0.45Ce0.45Na0.10O1.65-1.4 569 584
Comparative examples 2 Bi10Ce80Sr10Ox 608 627
Comparative examples 3 Bi10Ce50Pr40Ox 606 634
Catalytic test results show that state is made all has ratio to all material of embodiment 1 to 5 after heat ageing and just The low T of the material of comparative examples 1,2 and 350Value.
Structure is tested in catalysis after hydro-thermal process:
The following table 3 is shown after state and hydro-thermal process is just made with the of the invention three kind composition of method A measurement PM removal efficiency and comparative examples 3,4,5 and 6 composition PM removal efficiency.The composition of comparative examples 3 to 6 is made just At excellent catalytic activity is shown under state, however, on the contrary, the composition of comparative examples loses after hydrothermal aging Their catalytic activity is lost, this is contrasted with the embodiment of the present invention for still showing catalytic activity.
Table 3
Sample Composition T50Made of just [DEG C] T50[DEG C] of hydrothermal aging
Embodiment 1 Bi0.45Ce0.45K0.10O1.65-1.4 515 582
Embodiment 2 Bi0.40Ce0.40K0.20O1.4-1.2 510 595
Embodiment 3 Bi0.30Ce0.60K0.10O1.7-1.4 520 584
Comparative examples 4 Ce50K50Ox 468 655
Comparative examples 5 Ce50K50Ox 470 655
Comparative examples 6 Ce70K30Ox 464 672
Comparative examples 7 Ce70K30Ox 524 678
The effect for the miscellaneous difference Ce-Bi-M- mixed-metal oxides that potassium is mixed:
The following table 4, which is shown, removes PM with three kinds of difference Ce-Bi-M- mixed-metal oxides of the potassium doping of method B measurement Except the effect of efficiency.The doping of useful potassium composition after state and heat treatment is just made to the catalytic activity of soot oxidation It is all larger than undoped composition.
Table 4
Sample Composition T50Made of just [DEG C] T50[DEG C] of aging
Embodiment 1 Bi0.45Ce0.45K0.10O1.65-1.4 426 479
Embodiment 6 Bi0.4Ce0.4K0.1Sr0.1O1.55-1.35 414 490
Embodiment 7 Bi0.4Ce0.4K0.1Pr0.1O1.6-1.4 437 498
Embodiment 8 Bi0.4Ce0.4K0.1Fe0.1O1.6-1.4 414 507
Comparative examples 8 Bi45Ce45Sr10Ox 518 525
Comparative examples 9 Bi45Ce45Pr10Ox 458 508
Comparative examples 10 Bi45Ce45Fe10Ox 490 515
Detailed description of the invention (Fig. 1 to 2)
Fig. 1 shows the Powder x-ray diffraction figure of comparative examples 4, non-reflective reference CeO2And KNO3。
Fig. 2 shows the Powder x-ray diffraction figure of embodiment 1, non-reflective reference Ce1-xBixO2-x/2、α-Bi2O3And Bi2 (CO3)O2, do not detect crystalline potassium substance.

Claims (13)

1. a kind of composition of Formulas I,
Ce1-a-b-cNaMbDcOx I
Wherein
M represents potassium,
N is Bi and/or Sb,
D exists or is not present, if it is present selected from one or more of following element
-Mg,Ca,Sr,Ba；
-Y,La,Pr,Nd,Sm,Gd,Er；
-Fe,Zr,Nb,Al；
A is the number in the range of 0 < a≤0.9,
B is the number in the range of 0 <b≤0.3,
C is the number in the range of 0≤c≤0.2；
A adds b that c is added to be < 1, and
X is the number in the range of 1.2≤x≤2.
2. composition according to claim 1, wherein there are D.
3. composition according to any one of claim 1 or 2, wherein D is Ca, Sr, Ba.
4. composition according to any one of claim 1 or 2, wherein D is Y, Pr, La, Nd.
5. composition according to any one of claim 1 or 2, wherein D is Fe, Zr, Nb, Al.
6. composition according to any one of claim 1 or 2, wherein c is the number in the range of 0≤c≤0.1.
7. composition according to claim 1, wherein the composition has Formula II
Ce1-a-bNaMbOx II
Wherein
M represents potassium,
N is Bi and/or Sb,
A is the number in the range of 0 < a≤0.9,
B is the number in the range of 0 <b≤0.3,
A adds b to be < 1, and
X is the number in the range of 1.2≤x≤2.
8. according to claim 1, composition described in any one of 2 or 7, wherein N is Bi.
9. according to claim 1, composition described in any one of 2 or 7, wherein a is the number in the range of 0.01≤a≤0.9.
10. according to claim 1, composition described in any one of 2 or 7, wherein b is the number in the range of 0.01≤b≤0.3.
11. composition according to claim 10, wherein b is the number in the range of 0.1≤b≤0.2.
12. according to claim 1, composition described in any one of 2 or 7, wherein the composition is selected from by following composition The group of composition
Bi0.45Ce0.45K0.10O1.65-1.4,
Bi0.40Ce0.40K0.20O1.4-1.2,
Bi0.30Ce0.60K0.10O1.7-1.4,
Bi0.80Ce0.10K0.10O1.5-1.4,
Bi0.10Ce0.80K0.10O1.8-1.4,
Bi0.4Ce0.4K0.1Sr0.1O1.55-1.35,
Bi0.4Ce0.4K0.1Pr0.1O1.6-1.4, and
Bi0.4Ce0.4K0.1Fe0.1O1.6-1.4。
13. composition according to any one of claim 1 to 12 is used for diesel engine, gasoline engine, lean-combustion engine With the purposes of the exhausted gas post-processing system in power plant.
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